Continuous polyamidation process - i

ABSTRACT

A continuous process for the manufacture of a polyamide, the process comprising the steps of: (i) flowing a stream A comprising a molten dicarboxylic acid, or a molten dicarboxylic acid-rich mixture comprising a dicarboxylic acid and a diamine, through a first stage and at least one more reaction stage of a vertical multistage reactor, wherein the first stage is at the top of the reactor; (ii) counter-currently flowing a stream B comprising a diamine as either a vapour or a diamine-rich liquid through at least one of the stages below the first reaction stage of said vertical multistage reactor; (iii) accumulating a liquid phase material P comprising polyamide at and/or below the final stage of said reactor; wherein said reactor is equipped with internal features suitable for effecting contact between counter-currently flowing streams A and B; and wherein said process further comprises the step of agitating said liquid phase material P by injecting a gaseous stream C comprising steam, or at least one inert gas, or a mixture of steam and at least one inert gas into the reactor at or below the final stage of the reactor. The invention further provides a vertical multistage reactor configured to implement said process.

FIELD OF THE INVENTION

The present invention relates to methods for the production ofpolyamides, and apparatus in which the polymerisation process can beconducted. More particularly, the present invention relates tocontinuous processes for the production of high molecular weightpolyamides by the reaction of a dicarboxylic acid with a diamine viacounter-current flow in a vertical multistage reactor.

BACKGROUND OF THE INVENTION

Polyamides, such as nylon-6,6, require starting monomers of two kinds, amonomer having a pair of carboxylic acid functional reactive groups(diacid) and a monomer having a pair of amino functional reactive groups(diamine), and such polyamides are typically referred to as dimonomericpolyamides. The polyamide may further incorporate more than one diacidand more than one diamine and may incorporate a small amount, usually nomore than 10%, of a third kind of starting material having a carboxylicacid functional group and an amino functional group or a functionalprecursor to such a compound.

In a conventional method of preparing such dimonomeric polyamides, thestarting diacid and diamine components are mixed in stoichiometricproportions into an aqueous solution. The water is subsequently removedby evaporation, typically at elevated pressure in order to achieve ahigh enough boiling temperature to prevent the formation of solids.However, the post-evaporation pressure reduction step requires excessiveheat to prevent the product from solidifying, and this heating is knownto cause discoloration and chemical degradation of the product.

To avoid the use of water, alternative methods to produce polyamidescomprise the supply of one or both components in liquid (molten) form.Typically, the polyamidation reactions are carried out in verticalmultistage reactors, otherwise known as column reactors. The requisitediacid and diamine are flowed counter-currently through the reactor andthe product polyamide collects at the lowest stages of the reactor, orcolumn bottom. However, the high temperatures required to retain thecomponent(s) in melt form can result in degradation, and a number ofmethods (see, for instance, U.S. Pat. No. 4,131,712, U.S. Pat. No.4,433,146 and U.S. Pat. No. 4,438,257) have sought to reduce suchdegradation and overcome associated difficulties. U.S. Pat. No.5,674,974 (incorporated by reference herein in its entirety) disclosesthe continuous production of polyamide in a vertical multistage reactorwith counter-currently flowing dicarboxylic acid and diamine streams,which improved earlier processes by reducing energy consumption,reducing capital cost of equipment and reducing environmental emissions,as well as improving product quality. In vertical multistage reactorssuch as that disclosed in U.S. Pat. No. 5,674,974 the diacid feed streamtypically consists of a mixture of diacid and diamine in which there isan excess of diacid. Such a diacid feed-stream does not requiresupra-atmospheric pressures in order to solvate in the moisture producedby the polyamidation reaction, and thus the reactors are operated atatmospheric pressure. The flow of diamine fed into the reactor istypically controlled to maintain a stoichiometric balance of diacid anddiamine.

In all such methods comprising the supply of component(s) in liquid(molten) form, it is a requirement that the molten material accumulatingat the bottom of the reactor must be homogeneous and sufficiently mixed,in order for the reaction to proceed efficiently. Agitation is essentialto column operation in order to homogenize the lower three stages andavoid gel build-up in stagnant zones, which can also cause degradationand the formation of coloured impurities. Gel build-up occurs because,without direct means for controlling the chemical equilibria in themelt, the temperature rises due to the heat emitted by the polyamidationreaction which in turn causes evaporation of water produced by thepolyamidation reaction thus causing a rise in viscosity and gelbuild-up. For example, as the temperature reaches ca. 250° C. mid-waydown the column reactor the moisture in the liquid melt falls below ca.0.5 wt % and approaches 0.2 wt %. The melt is thus starved of moisture,thereby promoting viscosity rise. All such conventional processestherefore require mechanical agitation in order to attain sufficientmixing. However, there are several disadvantages associated with the useof mechanical agitation, including reactor complexity and complexity inprocess scale-up. Agitators used in vertical multistage polyamidationreactors are complicated and expensive to design and manufacture as theyrequire adequate mechanical strength to sufficiently agitate moltenpolyamide, but minimal surface area and roughness in order to limit theextent to which their surface provides nuclei for gelation. Largerreactors require commensurately larger mechanical agitators. However, asthe size of the agitator is increased to cope with the increased size ofthe reactor, it becomes increasingly difficult to transmit the torquegenerated by the agitator across the diameter of the column. Moreover,as the size of the mechanical agitator increases, its mechanicalstrength must also increase, which leads to difficulties in the design,fabrication and reliability of the component, as well as increasedcapital expenditure. The effective limit on the size of the mechanicalagitator in turn limits the size of the polyamidation reactor, and hencethe production output. In addition, processes and apparatus usingconventional mechanical agitation are sensitive to perturbations ofmaterial in the reactor, and can suffer from poor reliability.

It is an objection of the present invention to overcome one or more ofthese problems.

As used herein, the term “counter-currently flowing” has the meaningconventional in the art, namely the direction of the current of one flowstream is opposite to the direction current of another flow stream inthe reactor.

As used herein, the term “salt” is used in a general sense to encompassthe precursors to polyamidation whether in a fully ionized state, anoligomeric state, or in any combination thereof.

As used herein, the term “weir” has its meaning conventional in the art,namely a barrier which impedes the flow of liquid phase reaction fluid.The weir causes liquid phase reaction fluid to pool behind it, whileallowing liquid phase reaction fluid to flow steadily over the top of itonce a sufficient volume of reaction fluid has built up behind it. Thus,a weir preferably comprises a surface which is perpendicular orsubstantially perpendicular to the direction of flow of the liquid phasereaction fluid at the point of contact of the weir with the reactionfluid, although any appropriate angle greater than 0° (preferably atleast 30°, preferably at least 60°, preferably at least 85°) to thedirection of flow of the reaction fluid may be used.

SUMMARY OF THE INVENTION

According to the present invention, there is provided a continuousprocess for the manufacture of a polyamide, the process comprising thesteps of:

-   -   flowing a stream A comprising a molten dicarboxylic acid, or a        molten dicarboxylic acid-rich mixture comprising a dicarboxylic        acid and a diamine, through a first stage and at least one more        reaction stage of a vertical multistage reactor, wherein the        first stage is at the top of the reactor;    -   (ii) counter-currently flowing a stream B comprising a diamine        as either a vapour or a diamine-rich liquid through at least one        of the stages below the first reaction stage of said vertical        multistage reactor;    -   (iii) accumulating a liquid phase material P comprising        polyamide at and/or below the final stage of the reactor (i.e.        the stage furthest below said first stage of said reactor);        wherein said reactor is equipped with internal features suitable        for effecting contact between counter-currently flowing streams        A and B; and        wherein a gaseous stream C comprising steam, or at least one        inert gas, or a mixture of steam and at least one inert gas, is        injected into the reactor at or below said final stage.

According to a further aspect of the present invention, there isprovided a vertical multistage reactor, or column reactor, suitable forimplementing the process of the invention, wherein the reactorcomprises:

-   -   (i) a first stage;    -   (ii) at least one stage below the first stage;    -   (iii) internal features suitable for effecting contact between        counter-currently flowing streams of a first stream A introduced        through the first stage and a second stream B introduced through        at least one of the stages below the first reaction stage; and    -   (iv) a chamber configured to allow a gaseous stream C to be        injected from the chamber into the reactor at or below the final        stage of the reactor.

The process reduces or eliminates the requirement for direct mechanicalagitation in the lowest stages of the reactor compared to processesknown in the art. The invention provides a number of benefits, includingsimplified reactor designs, ease of process scale-up and design,increased reactor size and output, improved reactor balance, reductionsin sensitivity to perturbations in material in the reactor, increasedreliability, reduced energy requirements, lower capital expenditure ofequipment and improved heat transfer in the reactor.

The present invention may be used in a reactor entirely withoutmechanical agitation, or it may be used in conjunction with mechanicalagitation. One of the key advantages of the invention is that the sizeand output of the column reactor is no longer dependent on the size ofthe mechanical agitator. Furthermore, there is no longer a need tooperate at the limits of the mechanical strength of the agitator inorder to increase reactor size and output.

The present invention allows the production of polyamide with lowamounts of impurities and/or colorants more efficiently and moreeconomically

DETAILED DESCRIPTION OF THE INVENTION

The process of the present invention is carried out in a verticalmultistage reactor, known in the art as a column reactor. The verticalmultistage reactor may have up to 10 or more stages, typically 6 to 10stages. The first stage is at the top of the reactor (column top), andthe reactor has one or more additional stages below the first stage, thefinal stage (i.e. the stage which is furthest from the first stage)being at the bottom of the reactor (column bottom).

In the process of the present invention, molten diacid may be fed intothe reactor or a molten acid-rich mixture of diacid and diamine may befed into the reactor. A suitable acid-rich mixture is about 75% to about85% by weight diacid relative to the total amount of diacid and diaminein the mixture and about 15% to about 25% by weight diamine relative tothe total amount of diacid and diamine in the mixture. Such a process isparticularly applicable to the manufacture of nylon-6.6(poly(hexamethylene adipamide)) where the starting materials compriseadipic acid and hexamethylene diamine.

The composition of stream A introduced into the reactor may comprisedicarboxylic acid alone, and such a process is suitable for a diacidthat does not suffer excess degradation at a temperature around itsmelting point. The term “comprise” in this sense means that the stream Acontains at least 60% by weight dicarboxylic acid, preferably at least80% by weight and most preferably at least 95% by weight. Alternatively,stream A may comprise an acid-rich mixture which is introduced into thereactor, and the term “comprise” in this sense means that the stream Acontains at least 60% by weight acid rich mixture, preferably at least80% by weight and most preferably at least 95% by weight. Themolten-dicarboxylic acid-rich mixture comprises a dicarboxylic acid anda diamine, and similarly the term “comprise” in this sense means thatthe acid-rich mixture is at least 80% by weight of the combination ofdicarboxylic acid and a diamine, preferably 95% by weight, morepreferably greater than 99% by weight. In all alternatives for thestream A, the stream contains at least 4000 gram-moles of dicarboxylicacid per million grams of polyamide produced, preferably at least 5000.The dicarboxylic acid is combined with diamine to produce an acid-richmixture, which may be achieved continuously or batch-wise, suitably suchthat a steady flow to the first stage of the reactor is maintained.Molten dicarboxylic acid-rich mixtures comprising dicarboxylic acid anddiamine may be prepared by melting compositions (for example, particles,pellets, pastilles or flakes) having the desired mixture, such as thoseprepared in WO-2013/08574-A, which is incorporated by reference in itsentirety.

Preferably, diacid is combined with diamine into an acid-rich feedstream to provide a feed in which the diacid remains chemically stable,particularly where nylon 6,6, is the product and adipic acid is thedicarboxylic acid. This may be done continuously or batch-wise, suitablywherein a steady feed stream to the first stage of the reactor ismaintained. One method is provided in U.S. Pat. No. 4,131,712, col. 2,lines 30-39, which is incorporated herein by reference. A preferredmethod is to carry out that process continuously by combining feedstreams of solid, granular adipic acid and hexamethylene diamine orhexamethylene diamine solution (which is commercially used at 85-100%purity, balanced with water) at approximately 120° C. to 135° C. withagitation, suitably wherein the molten acid-rich feed is withdrawn atthe same rate as the feed streams.

A preferred method for preparing the acid-rich feed is disclosed inUS-5,674,974, the disclosure of which is incorporated herein byreference, and in particular the continuous process for preparing anessentially anhydrous mixture of diacid and diamine disclosed in thatdocument.

Diamine is fed into the reactor in the form of a liquid (preferably adiamine-rich liquid) or a vapour to at least one of the reaction stagesbelow the first stage. Preferably, diamine is fed into the reactor atthe final stage of the reactor and optionally one or more intermediatestage(s), preferably wherein said intermediate stage(s) are immediatelyabove the final stage. Preferably, diamine is added as vapour. If fed asa liquid, diamine undergoes substantial vapourization when it comes intocontact with the hot polymerizing mixture. Pre-vapourization of thediamine feed-stream removes some of the heat requirement from thereactor and reduces the likelihood of temporal variation in the amountof diamine vapour flow at various points in the reactor. Typically,diamine is fed into the reactor at a flow rate of at least about 40kg/hr, and up to about 10,000 kg/hr in large reactors. As the skilledperson will appreciate, the flow rate selected is dependent upon anumber of factors, including the reactor size, the amounts ofdicarboxylic acid or acid-rich mixture fed into the top of the reactor,the identities of the diacid and diamine, and the temperature of themelt, as discussed in more detail below.

An excess of free dicarboxylic acid over free amine is preferablymaintained in the reactor during the process at each stage of thereactor. The amount of the excess (i.e. the ratio of free dicarboxylicacid to free amine) decreases down successive steps of the reactor asdicarboxylic acid in the feed-stream to the top of the reactor reactswith diamine fed into the bottom of the reactor.

The absorption of diamine into a reactive polyamide liquid is most rapidand complete when the liquid is highly acid-rich and at a relatively lowtemperature. The rate of transfer of diamine from vapor into liquid issufficiently rapid and complete, even when the liquid is close to abalance of acid and amine ends, and at a high enough temperature to keephigh molecular weight polymer molten, so that a reactor with six toeight stages is capable of producing balanced polymer and at the sametime of retaining in the polymer essentially all of the diamine fed intothe reactor.

The balance of acid and amine functional reactive groups (ends) issuitably monitored and controlled by an appropriate controlling system.Preferably, the balance is monitored by near-infrared spectrophotometryin the manner described in U.S. Pat. No. 5,674,974 which is incorporatedherein by reference.

Holding time in the reactor is typically in the range from about onehour to about three hours.

In the vertical multistage reactors with which this invention isconcerned, a liquid phase material P comprising polyamide accumulates atthe bottom of the column, i.e. at and/or below the final stage, and thepolyamide reaction product is then collected from this liquid phasematerial P. According to the present invention, gaseous stream C isinjected into the reactor and through the liquid phase material P inorder to sparge said liquid phase material P, thereby attainingagitation thereof. The sparging-induced agitation prevents stagnation,which can cause degradation and/or the formation of gels and/or colouredimpurities, which detracts from the quality of the polyamide product.Stream C agitates the mixture and drives turbulence to attain sufficientmixing and reduce or eliminate the need for direct agitation. The amountof gas injected is at least about 5 kg/hr per million grams of polyamideproduced per hour, preferably at least about 8, and typically no morethan about 25, more typically no more than about 20. In conventionalprocesses, and in the absence of sparging, the natural vapour flow ratein the bottom stages of a column reactor is several times lower than inthe top stages. Augmenting with additional amounts of an inert gas orvapour also improves column balance and heat transfer.

The stream C may comprise, consist of, or consist essentially of steam.The stream may comprise, consist of, or consist essentially of an inertgas. The stream may comprise, consist of, or consist essentially of amixture of steam and at least one inert gas. The inert gas is suitablyselected from the group consisting of N₂ and Ar, although other inertgases known to those skilled in the art may be used. The flow rate ofthe gaseous stream C may be controlled to give the required degree ofagitation, and will depend upon a number of factors, including reactorsize, the identity of the reactants and the other process conditions.The flow rate of stream C is suitably modulated in order to controlwithin appropriate or pre-determined levels the total amount of waterwhich exits as vapour/steam at the top of the reactor, bearing in mindthat water is also a product of the polyamidation reaction.

The gaseous stream C may also have the effect of sparging liquid phasematerial accumulating at other stages in the reactor, i.e. at stagesbelow the first stage and above the final stage, in order to agitate andattain sufficient mixing in these stages also. This effect is typicallymore significant for the lower stages closest to the bottom of thereactor and less significant for the upper stages closest to the top ofthe reactor. It will be appreciated that gaseous stream C is introducedinto the reactor in order to agitate the liquid phase material P that isaccumulating at and/or below the final stage of the reactor, and hencethe gaseous stream C is introduced at the lowest point of the reactor atwhich liquid phase material P accumulates. Typically, therefore, thegaseous stream C is introduced at least below the final stage of thereactor, which is typically below the lowest point of entry of thediamine.

Gaseous stream C is preferably injected into the reactor via one or moreinlets from a pressurized gaseous chamber, or plenum. The plenum ispreferably located at or below the final stage, i.e. the column bottom.

The temperature of the first stage and any other further stages shouldbe sufficiently high to prevent solid forming in the reactor.Preferably, the temperature of the first stage and subsequent stages isat least about 125° C., preferably at least about 140° C., and may be atleast about 160° C. or at least about 160° C., and preferably no morethan about 180° C. Preferably, the temperatures of the second andsubsequent stages of the reactor are greater than that of the firststage, such that the temperature of the reaction fluid is increasedgradually as it passes from stage to stage down the column reactor.Preferably the temperature of the second and any subsequent stages is atleast about 210° C., preferably at least about 215° C. Preferably thetemperature of the second stage is no more than about 230° C.,preferably no more than about 225° C. Preferably, the temperature in thefinal stage is at least about 260° C., and may be at least about 270°C., and preferably no more than about 280° C. Such temperature rangesare particularly suitable for the production of nylon 6.6, and may bemodified as appropriate for other polyamides.

The reactor is operated under atmospheric pressure or below atmosphericpressure (i.e. under an applied vacuum), and is preferably operatedunder atmospheric pressure. By “operated under atmospheric pressure” ismeant that the material pooling at the first stage of the column reactor(i.e. the furthest stage from the bottom of the column) is venting atatmospheric pressure. The pressure is measured in the vent line locatedat the top of the reactor where gaseous material is vented from thereactor. As the skilled person will nevertheless appreciate, thepressure will be greater at the bottom of the column because of theweight of the liquid above.

Preferably, the viscosity of the liquid phase material P is maintainedat a value of no more than about 1200 poise, preferably no more thanabout 500 poise, and preferably in the range of from about 0.1 to about200 poise.

Viscosity may be controlled by directly controlling the chemicalequilibrium of the polyamidation reaction in the reactor. In particular,the limit of viscosity may be controlled by limiting the chemicalequilibrium of the polyamidation reaction in any specific stage of thereactor by altering the composition of that stage. As used herein, theterm “controlling the chemical equilibrium” means controlling therelative rates of the forward and reverse reactions of the equilibrium.

In a preferred embodiment, viscosity is controlled by injecting a streamcomprising steam into at least one of the stages below said firstreaction stage of the vertical multistage reactor. The stream comprisingsteam may be said stream C, or may alternatively be a stream D which isinjected into at least one of the stages below said first reaction stageof said vertical multistage reactor. Stream D may be injected into thereactor to sparge said liquid phase material P. Preferably, stream Dfurther comprises at least one inert gas, suitably selected from thegroup consisting of N₂ and Ar, although any inert gas known to thoseskilled in the art may be used as appropriate. The flow rate of thestream D will depend upon, inter alia, reactor size, the identity of thereactants and other process conditions, and is suitably modulated inorder to control within appropriate or pre-determined levels the totalamount of water which exits as vapour/steam at the top of the reactor,bearing in mind that water is also a product of the polyamidationreaction. In the polyamidation reaction of the process of the invention,the introduction of steam forces the equilibrium in the direction of thereactants, and this occurs where conditions are favourable forabsorption of the steam into the melt (typically towards the upperstages of the reactor, rather than in the bottom stages of the reactorwhere the melt temperature may be too hot for absorption to occur). Itwill further be appreciated that increasing the moisture content(humidity) above the melt in the reactor in accordance with the presentinvention reduces the rate at which water vapour escapes from the melt,thereby impeding the rate of the polyamidation. Thus, the chemicalequilibrium can be controlled through the moisture concentration of themelt by the introduction of steam into the reactor. Thus, theintroduction of steam into the reactor in this way provides control overthe viscosity of the liquid phase material in the reactor and over theviscosity of the liquid phase material P which is ultimately produced bythe column reactor.

Alternatively or additionally, viscosity is controlled by maintainingthe pressure of the reactor at a pressure greater than atmosphericpressure, preferably at least about 1.5 atm, preferably at least about 2atm, preferably at least about 5 atm, and preferably no more than about20 atm, preferably no more than about 17 atm, preferably no more thanabout 12 atm. In the polyamidation reaction described herein, increasingthe pressure forces the equilibrium in the direction of the reactants,at least in a closed reactor. Thus, the chemical equilibrium can becontrolled through the moisture concentration of the melt by controllingthe pressure in the reactor. Again, it will be appreciated thatincreasing the moisture content (humidity) above the melt in the reactorin accordance with the present invention reduces the rate at which watervapour escapes from the melt, thereby impeding the rate of thepolyamidation. Thus, controlling the pressure in the reactor providescontrol over the viscosity of the liquid phase material in the reactorand over the viscosity of the liquid phase material P which isultimately produced by the column reactor. Conventional co-currentreactors require pressurised reactors (normally above about 13 atm) inorder to preclude precipitation or crystallisation of salt in thereactor, i.e. by controlling temperature and pressure during thereaction the conventional co-current reactors utilise moisture in themolten reaction fluid to solvate the salt and the polymer of thebalanced feeds. In the counter-current process of the present invention,solvation is not required, and pressurisation of the column reactor iseffected not for the purpose of solvation but in order to control thechemical equilibrium.

Directly controlling the chemical equilibrium of the polyamidationreaction either by the introduction of steam or by the pressurisation ofthe reactor, as described above, determines the moisture concentrationof the melt. Preferably, the moisture concentration of the melt (i.e.the liquid reaction material in the reactor) is maintained at a levelsuch that the moisture concentration of the liquid phase material P isgreater than about 0.1 wt %, preferably at least about 0.2 wt %,preferably at least about 0.3 wt %, and preferably no more than about3.0 wt %. In conventional processes, as the temperature increases downthe column reactor, the moisture concentration in the liquid meltdecreases, thereby encouraging viscosity rise which would otherwise becontrolled and limited only by residence time in the column, hence therequirement for mechanical agitation to prevent gelation in stagnantsections of the column. In the present invention, controlling moistureconcentration by controlling the chemical equilibrium via steamintroduction or pressurisation enables the process to reduce oreliminate the need for the mechanical agitation of conventionalprocesses.

Alternatively or additionally, the viscosity of the liquid phasematerial is controlled by controlling stream B so that the amounts ofdiamine and dicarboxylic acid introduced into the reactor during theprocess are stoichiometrically imbalanced. In particular, an excess ofdicarboxylic acid over diamine is introduced into the reactor during theprocess. Thus, the column reactor is starved of diamine. Viscosity risein the reactor results from increasingly greater amounts of polyamideproduct and an increasingly higher degree of polymerization of thatproduct as the reaction progresses from the top stage to the bottomstage, and viscosity rise also results from the evaporation of the waterproduced by that polyamidation reaction. According to this aspect of theinvention, the final viscosity of liquid phase material P can becontrolled within pre-determined and desirable limits by controlling theamount of diamine introduced into the reactor. Thus, the polyamideproduct of liquid phase material P is itself stoichiometricallyimbalanced, and comprises an excess of acid end-groups over amineend-groups. As used herein, the term “stoichiometrically imbalanced”defines the molar ratio of [moles dicarboxylic acid units]:[moles ofdiamine units] wherein the molar ratio is different from 1.0, andpreferably greater than 1.0. A stoichiometrically imbalanced polyamidecomprises an excess of acid end-groups over amine end-groups or viceversa, and preferably comprises an excess of acid end-groups over amineend-groups. Preferably, such stoichiometric imbalance in the liquidphase material P is such that this molar ratio is no more than 1.3:1,preferably no more than 1.1:1, and preferably no more than 1.05:1, andpreferably at least 1.005:1.

The three methods of controlling viscosity described hereinabove may beused separately from each other, or they may be used in combination.Thus, the viscosity of the liquid phase material may be controlled bymeans of either steam introduction or by pressurisation or bystoichiometric imbalance. Alternatively, viscosity is controlled bysteam introduction in combination with either pressurisation orstoichiometric imbalance. Alternatively, viscosity is controlled bypressurisation in combination with stoichiometric imbalance, optionallyin combination with steam introduction.

The vertical multistage reactor is equipped with internal featuressuitable for effecting contact of counter-currently flowing diamine withthe molten dicarboxylic acid or acid-rich feed stream so as to achieverapid, efficient scrubbing of the diamine from the counter-currentlyflowing vapour. Such internal features are preferably present in eachstage of the reactor.

Suitable internal features are suitably selected from perforated platesand coils to allow counter-current flow of diamine vapour and steamand/or inert gas from their entry points at the bottom of the columnreactor and/or the lower stage(s) thereof towards the first and/or upperstage(s) of the reactor. Perforations are of sufficiently small diameterto allow passage of vapour in counter-current flow but without allowingpassage of the liquid phase reaction fluid in the co-current directionof flow. Perforations may be present in a plate and/or a coil.

In a preferred embodiment, each stage comprises a substantiallyhorizontal plate, one or more substantially vertical channel(s) and oneor more weir(s), to effect contact between counter-currently flowingstreams A and B. A vertical channel is also referred to herein as a“downcomer”.

Liquid phase reaction fluid pools on the substantially horizontal plateuntil it reaches a level such that the reaction fluid flows over theweir(s) and down the substantially vertical channel(s), and then intothe next stage. In such a state, the stage is referred to as beingflooded. The amount of reaction fluid in each stage reaches a steadystate during operation of the continuous process. In such a state theweirs are typically submerged in the reaction fluid. The fluid flowsdown said vertical channel(s) onto the substantially horizontal plate ofthe stage below. Preferably said one or more weir(s) is/are at the topof said vertical channel(s) and the fluid flows over the weir(s)directly into the channel(s). The height of a weir determines the degreeto which it impedes the flow of liquid reaction fluid (referred toherein as “liquid hold-up”). The height of a weir is such that itattains optimal hold-up of the liquid phase reaction material, andsuitable for the reactor size and the flow rate of the reaction materialthrough the reactor. Thus, each stage is in fluid communication with anadjacent stage via said vertical channel(s), such that liquid phasereaction fluid flows from one stage to an adjacent stage down saidvertical channel(s).

Each substantially horizontal plate comprises perforations which allowpassage of gas, but not liquid phase reaction fluid. The perforationshave a diameter appropriate for the nature and identity of the liquidphase reaction material, and the process conditions (including, interalia, the flow rate of sparging gas and diamine). Thus, each stage is infurther fluid communication with an adjacent stage via perforations,such that vapour flows counter-currently from one stage to an adjacentstage through the perforations. For example, diamine fed into the lowerstages of the reactor passes upwardly through the perforations and isscrubbed by diacid in the liquid phase reaction material that is poolingon the horizontal plates. Gas that is injected to sparge the liquidphase reaction material at the bottom of the column may also passthrough the apertures and sparge the liquid pooling on the pates inorder to provide agitation of the liquid pooling on the plates andreduce or prevent gelation in stagnant zones.

A vertical channel may be defined by walls which extend downwardly tothe upper surface of the horizontal plate of a subsequent stage, inwhich case perforations in a wall of the vertical channel allow reactionfluid to pass from the vertical channel onto the horizontal plate.Alternatively, a wall defining at least in part a vertical channel doesnot extend to the upper surface of the horizontal plate of a subsequentstage, allowing reaction fluid to pass through the gap between thebottom of a wall of the vertical channel and the horizontal plate of thesubsequent stage

In a preferred embodiment, and as illustrated in in FIG. 2b , adjacentstages have two different and alternating configurations. In a firstconfiguration, stage (n) comprises a horizontal plate extending inwardlyfrom the walls of the reactor across the cross-section of the reactorcolumn to define an opening and further comprises a downcomer locatedwithin said opening, wherein said opening is preferably substantiallyaligned with the centre of the plate. The top end of the downcomerextends above the plane of the horizontal plate to form the weir.Typically, the wall of the weir extends not only above the plane of thehorizontal plate but also below the plane of the horizontal plate sothat the downcomer is defined by an extended vertical channel. Liquidphase reaction fluid pools on the horizontal plate and flows over thetop edges of the downcomer into the vertical channel defined thereby andthen flows down onto the horizontal plate of the subsequent stage (n+1)below. In this first configuration of the stage (n), the flow ofreaction fluid in the stage is inwardly from the walls of the reactortowards a central vertical channel. The subsequent stage (n+1) has asecond configuration, in which the horizontal plate extends outwardlyfrom the central axis of the reactor across only part of thecross-section of the reactor column to define an annular opening betweenthe horizontal plate and the walls of the reactor. A weir is disposedaround the circumference of the plate. There is no cylindrical downcomerat the centre of the plate in this second configuration, and instead avertical channel is provided by the cylindrical annulus defined by thewall of the reactor and the wall of the weir. Again, the wall of theweir extends not only above the plane of the horizontal plate but alsobelow the plane of the horizontal plate to define an extended verticalcylindrical annular channel. Reaction fluid pools on the horizontalplate of said stage (n+1) until it flows over the weir and down thevertical cylindrical annular channel into next stage (n+2), whichrepeats the first configuration described above for the stage (n). Theflow of reaction fluid in the second configuration of the stage (n+1) isthus outwardly from the centre of the reactor.

In a further preferred embodiment, and as illustrated in FIG. 2a , astage comprises a horizontal plate which extends from a portion of thereactor wall across a portion of the cross-section of the reactor todefine an opening bounded by a first arc defined by the boundary of thehorizontal plate and a second arc defined by the internal surface of thewall of the reactor, preferably wherein the first and second arc areconcentric. The area of a horizontal surface of said plate is thusreduced, relative to the cross-sectional area of the column reactor, byan arc-shaped opening along a portion of the circumference of thehorizontal plate. The angles of the first and/or second arcs may be thesame or different, and are preferably the same, and preferably saidangles are no more than 180°. The width of the opening is preferably thesame at all points around the arc, although tapered openings may also beused. At the boundary of the horizontal plate and the opening, there isdisposed around the opening a weir extending above the plane of thehorizontal plate, and preferably the walls of the weir also extend belowthe plane of the horizontal plate, thereby defining a vertical channelprovided by an arc of the cylindrical annulus defined by the wall of thereactor and the walls of the weir. Liquid phase reaction fluid pools onthe horizontal plate and flows over the top edges of the weir into thevertical channel and then flows down onto the horizontal plate of thesubsequent stage immediately below. The subsequent stage is suitablydisposed in the reactor such that its arc-shaped opening is on theopposite side of the reactor (i.e. diametrically opposed) to thearc-shaped opening of the immediately preceding stage.

The vertical channel comprises an opening (i.e. the diameter of acylindrical pipe or the width of an annular channel) which has a sizedetermined by, inter alia, the reactor size, the composition of thereaction material and the process conditions. As noted herein, one ofthe objects of the present invention is increased reactor size andoutput.

A stage may optionally comprise means to prevent or reduce entry ofvapour into said vertical channel(s), which might otherwise disrupt thedown-flow of the liquid phase reaction fluid through the channel.Suitable means comprises, for instance, a plate disposed substantiallyperpendicularly to the axis of the vertical channel and below the loweropening of said channel. Such means are referred to herein as vapourdeflectors. A vapour deflector may be used, for instance, in a stageconfigured according to the first or second configuration describedabove, and finds particular utility in the first configuration.

It will be understood by the skilled person that the internal featuresare attached to the reactor walls via appropriate mechanical fixings.

Advantageously, the process of the present invention can be used toeliminate the need for mechanical agitation at or below the final stageof the vertical column reactor.

However, the present invention can advantageously also be used incombination with mechanical agitation, and in particular in combinationwith a mechanical agitator having a size much smaller than wouldotherwise be required, for a given size of reactor, than in conventionalprocesses. As such, the prior art limitations on reactor size and outputare obviated. Equally, the present invention obviates the need forincreasingly larger agitators having the required combination of surfaceproperties and sufficient mechanical strength which would be needed forincreased reactor size and output, and such larger agitators would beenormously expensive and unreliable, even if they could be fabricated inthe first place. The sparging provided in the reactor and processaccording to the present invention instead allows a mechanical agitatorof much smaller size to be used in the reactor.

Thus, the present invention allows larger reactors to be built which inturn have larger polyamide output.

Thus, in one embodiment, the process of the present invention furthercomprises the step of mechanical agitation of the liquid phase materialP at or below the final stage of the reactor. Suitably, any mechanicalagitator is located in a conical region below the final stage and at thebottom of the reactor, as is conventional in the art.

The process herein can be used to produce a wide variety of polyamides,particularly dimonomeric polyamides, as well as copolyamides, dependingon the choice of diacids and diamines. The term “dimonomeric polyamide”as used herein refers to a polyamide prepared by the condensationpolymerization of only two monomers, a diacid and a diamine,

The diamine can be selected from the group consisting of ethanoldiamine,trimethylenediamine, putrescine, cadaverine, hexamethyelenediamine(HMD), 2-methyl pentamethylenediamine, heptamethylenediamine, 2-methylhexamethylenediamine, 3-methyl hexamethylenediamine,2,2-dimethylpentamethylenediamine, octamethylenediamine, 2,5-dimethylhexamethylenediamine, nonamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamines, decamethylenediamine, 5-methylnonanediamine,isophoronediamine, undecamethylenediamine, dodecamethylenediamine,2,2,7,7-tetramethyl octamethylene diamine, meta-xylylene diamine,paraxylylene diamine, bis(p-aminocyclohexyl)methane,bis(aminomethyl)norbornane, any C₂-C₁₆ aliphatic diamine optionallysubstituted with one or more C₁ to C₄ alkyl groups, aliphatic polyetherdiamines and furanic diamines such as 2,5-bis(aminomethyl)furan.

The dicarboxylic acid can be selected from the group consisting ofoxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid,adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioicacid, dodecandioic acid, maleic acid, glutaconic acid, traumatic acid,and muconic acid, 1,2- or 1,3-cyclohexande dicarboxylic acids, 1,2- or1,3-phenylenediacetic acids, 1,2- or 1,3-cyclohexane diacetic acids,isophthalic acid, terephthalic acid, 4,4′-oxybisbenzoic acid,4,4-benzophenone dicarboxylic acid, 2,6-napthalene dicarboxylic acid,p-t-butyl isophthalic acid and 2,5-furandicarboxylic acid.

In a preferred embodiment, the dicarboxylic acid is adipic acid and thediamine is hexamethylene diamine. Preferably, the process of the presentinvention is a process for the production of nylon-6,6.

An optional third starting material, having a carboxylic acid functionalgroup and an amino functional group or a functional precursor to such acompound, may also be used, and such materials are suitably selectedfrom 6-aminohexanoic acid, caprolactam, 5-aminopentanoic acid,7-aminoheptanoic acid and the like.

In addition to dimonomeric polyamides based solely on diacid anddiamines, it is sometimes advantageous to incorporate other reactants.When added at proportions less than 20% by weight, these may be addedinto the dicarboxylic acid or acid-rich mixture at some point prior tointroduction into the reactor. Such reactants may include monofunctionalcarboxylic acids such as formic acid, acetic acid, propionic acid,butyric acid, valeric acid, benzoic acid, caproic acid, enanthic acid,octanoic acid, pelargonic acid, capric acid, undecanoic acid, lauricacid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid,sapienic acid, stearic acid, oleic acid, elaidic acid, vaccenic acid,linoleic acid, erucic acid and the like. These may also include lactamssuch as α-acetolactam, α-propiolactam, β-propiolactam, γ-butyrolactam,δ-valerolactam, γ-valerolactam, caprolactam and the like. These may alsoinclude lactones such as α-acetolactone, α-propiolactone,β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone,caprolactone, and such like. These may include difunctional alcoholssuch as as monoethylene glycol, diethylene glycol, 1,2-propanediol,1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol,etohexadiol, p-menthane-3,8-diol, 2-methyle-2,4-pentanediol,1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. Higherfunctionality molecules such as glycerin, trimethylolpropane,triethanolamine and the like may also be useful. Suitable hydroxylaminesmay also be selected such as ethanolamine, diethanolamine,3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol,3-amino-1-butanol, 2-Amino-1-butanol, 4-amino-2-butanol, pentanolamine,hexanaolamine, and the like. It will be understood that blends of any ofthese reactants may also be utilized without departing from thisinvention.

It may also be advantageous to incorporate other additives into thedicarboxylic acid or acid-rich mixture at some point prior tointroduction into the reactor. These additives may include heatstabilizers such as copper salts, potassium iodide, or any of the otherantioxidants known in the art. Such additives may also includepolymerization catalysts such as metal oxides, acidic compounds, metalsalts of oxygenated phosphorous compounds or others known in the art.Such additives may also be delustrants and colorants such as titaniumdioxide, carbon black, or other pigments, dyes and colorants known inthe art. Additives used may also include antifoam agents such as silicadispersions, silicone copolymers, or other antifoams known in the art.Lubricant aids such as zinc stearate, stearyl erucamide, stearylalcohol, aluminum distearate, ethylene bis-stearamide or other polymerlubricants known in the art may be used. Nucleating agents may beincluded in the mixtures such as fumed silica or alumina, molybdenumdisulfide, talc, graphite, calcium fluoride, salts of phenylphosphinateor other aids known in the art. Other common additives known in the artsuch as flame retardants, plasticizers, impact modifiers, and some typesof fillers may also be added into the molten imbalanced mixtures priorto solidification. It will be understood that blends of any of thesereactants may also be utilized without departing from the fundamentalsof the embodiments disclosed herein.

It will be appreciated by the skilled person that the appropriateprocess conditions for performance of the invention will depend on thestarting materials, i.e. the dicarboxylic acid and diamine. Forinstance, an appropriate initial melt temperature for the feed-stream Awill depend on the identity of the dicarboxylic acid or acid-richmixture. In addition, it is known in the prior art (see, for instance,U.S. Pat. No. 4,131,712) that the initial melt-temperature (i.e. thetemperature of the melt of stream A fed into the top stage of thereactor) is suitably selected according to the diacid:diamine ratio ofan acid-rich mixture. Thus, as the temperature of the melt at the top ofthe column is increased, an increasing proportion of the volatilediamine is released from the top of the column. As the temperature ofthe melt at the top of the column is decreased, the greater is therequirement for heat input from the downstream heaters in subsequentstages of the column.

Where the feed material is a dicarboxylic acid-rich mixture, the skilledperson will appreciate that the diacid:diamine ratio and the reactiontemperature and pressure are inter-dependent. Thus, as thediacid:diamine ratio is decreased, the temperature at the top of thecolumn must be correspondingly increased to achieve a molten reactionmaterial with a useful viscosity, but as the temperature is increased,then increasing amounts of diamine are released from the top of thereactor by evaporation, and there is also an increasing likelihood ofthermal degradation of the reactants and reaction product. As notedabove, the reactor is preferably operated at atmospheric pressure, andthe diacid:diamine ratio is therefore selected accordingly. In analternative embodiment, the reactor may be a pressurised reactor, inwhich case lower diacid:diamine ratios may be used. Appropriatediacid:diamine ratios will therefore be apparent to the skilled person,and will vary according to the identity of the diacid and the diamine.For instance, where the diacid is adipic acid (AA) and the diamine ishexamethylene diamine (HMD), the feed material is preferably selectedsuch that the diacid:diamine ratio is greater than 0.6:0.4 for a reactoroperated under atmospheric pressure. At AA:HMD ratios as low as 0.6:0.4,the melt temperature would have to be increased to an extent that wouldresult in undesirable evaporation of HMD from the reactor, and in thatinstance a pressurised reactor would be appropriate.

The feed rate of the material introduced at the top of the reactor, andwhere appropriate the selection of the diacid:diamine ratio in thismaterial, determines the flow rate of the diamine reactant introducedinto the lower stages of the reactor, in order to obtain balance of theacid and amine components in the polyamide product P withdrawn at thebottom of reactor. The process conditions may optionally be selectedsuch that the polyamide product P comprises a slight excess of acid. Theappropriate diamine flow rate is therefore easily calculable by theperson skilled in the art. In practice, the feed rates ofdiacid-containing material and diamine introduced into the column arecalculated by the desired output of polyamide product P from thereactor, which in turn will vary according to the size of the reactor.

As the polyamidation reaction progresses, the diamine:diacid ratiochanges in successive stages down the column, and may be measured viathe parameter of “difference in end-groups” (DE), i.e. DE=[amount ofacid ends]−[amount of amine ends]. As the reaction material approachesthe bottom of the reactor, the material approaches stoichiometricbalance. In a preferred embodiment, the polyamide material P leaving thereactor comprises a slight excess of acid, which is then neutralisedafter polyamide P has exited the reactor by a “trim feed” of diamine,the amount of diamine required in the trim feed preferably beingcalculated based on near infra-red (NIR) spectroscopic measurements ofthe composition of the polyamide P leaving the reactor, as disclosed inU.S. Pat. No. 5,674,974. Preferably, the specification of the polyamideproduct P is such that DE is ±150 meq/kg, preferably ±100 meq/kg,typically from ±10 to 50 meq/kg, particularly wherein there is an excessof acid end-groups over amine end-groups. Preferably, the amount ofdiamine in the trim feed is calculated in order to obtain stoichiometricbalance, but the balance may be varied depending on the desiredspecification of the polyamide product.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 describes diagrammatically the internal configuration of aconventional polyamidation reactor. The reactor is divided into discretestages A to H using perforated barriers, (i) to (vii), between stages,which barriers allow separate passages for vapour and liquid flows fromstage to stage.

FIGS. 2a and 2b illustrate stage configurations that may be used inaccordance with the present invention. In FIG. 2a , each stage comprisesa substantially horizontal plate (4), a weir (5) and channel (6) definedin part by the wall (7) of the reactor. In FIG. 2b , alternate stagescomprise a first configuration (8) comprising a substantially horizontalplate (9) that extends inwardly from the wall (10) of the reactor with acentrally aligned cylindrical downcomer (11), the top of the downcomerproviding the weirs (12). Alternate stages in FIG. 2b comprise a secondconfiguration (13) comprising a substantially horizontal plate (14)extending outwardly from the central axis of the reactor and a verticalchannel (15) formed between weirs (16) and the wall (10) of the reactor.

FIG. 3a is a cross section of an eight stage vertical multistage reactoraccording to the present invention in use with the stage configurationsshown in FIG. 2b . The multistage reactor may also be used with thestage configurations shown in FIGS. 2a , or any other suitable plateconfiguration.

In FIG. 3a , feed material streams (17) and (19) are fed into mix tank(21) for diacid-rich feed preparation. The acid-rich feed is then fedinto stage/at the top of the reactor. The column is heated by heatsources (22) to (28). Agitator (30) is located at the bottom of thereactor. Hexamethylene diamine vapour is fed into the reactor at variousstages VI, VII and VIII. Nylon-6.6 polymer is removed after bottom stageVIII. Each stage comprises plates (34 or 34 a) comprising perforations(32) which allow flow of vapour but not liquid. The reaction liquidflows through each stage as shown in FIG. 3b , described in furtherdetail below.

Hexamethylene diamine is supplied as vapour continuously into the upperpart of each of the three stages (VI, VII and VIII) above the bottomstage. This vapour and any additional vapour of diamine or steam formedwithin the reactor flows from each stage to the stage above throughperforations (32) in substantially horizontal plates (34 or 34 a), thusbringing vapour into intimate contact with the liquid in the stageabove. The balance in the liquid phase material P is monitored by IRspectrometer (36) and the amount of hexamethylene diamine fed into thereactor is adjusted accordingly. Vapour flowing through the top stage iscontinuously removed from the top of the reactor.

Plenum (38) provides pressurised steam that is injected into the reactorthrough one or more inlets (40) to contact the liquid accumulating atthe bottom stage of the column in conical region (42) in order to spargethe liquid and reduce the need for mechanical agitation. Sparging gasbubbles out of the liquid at the bottom of the column and up throughperforations (32) in the stages thereabove, thereby also sparging theliquid pooling present in these stages and preventing gelation in thestagnant areas, although this effect is typically significant only inthe lower stages rather than the higher stages. Steam flowing throughthe top stage is continuously removed from the top of the reactor withdiamine and steam formed in the reactor.

FIG. 3b illustrates stages IV to VI in the column of FIG. 3a . In stagesIV and VI, the liquid phase reaction fluid (60) pools on horizontalplate (34 a) and flows in the direction (50) over weir (44) downcylindrical downcomer (48). In stage V, the liquid phase reaction fluidpools on horizontal plate (34) and flows over weir (54) down annularchannel (56) between weir (54) and the wall (58) of the reactor. In acontinuous process, the levels (59) of liquid phase reaction fluid areheld above the height of the weir such that the stage is flooded. Theheights (H_(a) and H_(b)) of weir (44) and weir (54) control the hold-upof liquid phase material in the reactor. Vapour deflector (62) preventsgas from flowing up through the channel (48) and disrupting liquid flow.

FIG. 3c is a plan view of horizontal plate (34 a) shown in FIGS. 3a and3b showing perforations (32).

FIG. 3d illustrates the bottom of the column shown in FIG. 3a . Liquidphase material P rich in high molecular weight polyamide accumulates inconical region (42) and is extracted from the reactor through outlet(60). Steam is injected from plenum (38) into the conical region tosupplement the agitation provided by mechanical agitator (30). Vapourdeflector plate (62) is located beneath channel (64) to prevent gas fromflowing up through the channel (64) and disrupting liquid flow. A pocketof sparging gas (66) typically forms beneath perforated plate (34 a),which then passes through perforations (32) towards the upper stages.

FIG. 3e illustrates a further design for the bottom of the column shownin FIG. 3a , wherein the plenum has an alternative configuration to theone shown in FIG. 3d . In particular, there are multiple entry points(68) form the plenum into the conical region (42).

FIG. 3f illustrates a further design for the final stage and the bottomof the column, suitable for replacing stage VIII and the column bottomof the reactor in FIG. 3a . At this lowest stage, liquid reactionmaterial (70) flows down annular channel (72) in the direction of arrows(74 a) and (74 b). The gaseous stream C of the present invention isinjected into the bottom of the reactor from plenum (76) through one ormore inlets (78), and suitably gaseous stream C is pressurised steam.Inlets (78) may also be used to introduce diamine vapour into thereactor at this point, optionally in combination with additional diamineinlets in higher stages (not shown) of the reactor as describedhereinabove. Inlets (78) may provide a combination of diamine vapour andgaseous stream C or pure diamine vapour or pure gaseous stream C. Theliquid phase material P flows over weir (80) and down channel (82) inthe direction of arrows (74 c), (74 d) and (74 e). An agitator (notshown) may be present in the channel (82) to agitate the material P inthe channel. The material P surrounding the channel is not agitated. Thegaseous component(s) introduced via inlets (78) pass up through theliquid phase material P in the direction of arrows (84 a) and (84 b),and then on to the preceding stage as described hereinabove. It will beappreciated that in this final stage only, there is co-current flow ofdiamine with the liquid reaction material at the bottom of the reactor.As the vapour travels in the direction of arrows (84 b) and up throughthe preceding and higher stages of the reactor, the diamine streamtravels counter-currently to the liquid/molten phase through thepreceding and higher stages of the reactor. The inner cone or cylinder(86) formed by weirs (80) is optionally agitated by a mechanicalagitator (not shown). Optionally, one or more apertures or gaps (notshown) are present at the base of the cone or cylinder (86) to allow asmall amount of liquid drainage bypassing the weir (80) thus reducingany tendency towards long liquid residence times in that zone.

FIG. 3g illustrates a further design for the final stage and the bottomof the column, suitable for replacing stage VIII and the column bottomof the reactor in FIG. 3a . The diameter 88 of the stage is reducedgradually to a smaller diameter 90, i.e. it is “necked down”. 94 is adowncomer from the stage above. The mechanical agitator 92 is onlypresent in the part of smaller diameter 90. Therefore, in the case oflarge columns, agitators having a smaller diameter than that of theupper stages of the column can be used. The reduction in diameter of thelowest stage and the mechanical agitator is possible due to spargingand/or control of the viscosity of the liquid phase material P by themethods disclosed herein.

The invention is further illustrated by the following non-limitingillustrative example for the production of nylon-6.6.

Example 1

Adipic acid (AA) and hexamethylene diamine (HMD) are fed into a mixingtank at 162 lb/hr and 38 lb/hr, respectively. The heated mixture is fedinto the top of an eight-stage reactor column at a rate of 199 lb/hr.Gaseous HMD is fed into the lowest three stages of the reactor at a rateof 90 lb/hr. During the reaction process, a stream C of steam is fedfrom a pressurised plenum at a rate of up to 20 lb/hr into a conicalchamber below the lowest stage at the bottom of the reactor, the conicalchamber being the region below the lowest stage in which is accumulatedliquid phase material P rich in high molecular weight polyamide. Thereactor is not equipped with an agitator, but otherwise comprises thefeatures described in FIGS. 3a to 3 d.

During operation of the reactor according to the invention, gaseoussteam exits from the top of the reactor at a rate of 40 lb/hr withoutadditional steam from stream C, or 60 lb/hr with additional steam fromstream C, wherein the vapour exiting the top of the reactor comprisesless than 100 ppm HMD. The reaction conditions of the process, theviscosity, the difference in end-groups and the molar amount of HMD ateach stage are shown in Table 1 below.

TABLE 1 Difference in HMD Stage Temp. Viscosity^(a) End-groups (meq/Kg)(mol %)^(a) 1 170° C. 0.3 Poise  9614 14.8 2 220° C. 0.5 Poise  961414.8 3 230° C. 1 Poise 8876 16.6 4 250° C. 2 Poise 6251 23.9 5 265° C. 5Poise 2482 37.7 6 275° C. 10 Poise  892 45.2 7 275° C.  20 P/10RV 3549.8 8 275° C. 100 P/17RV 35 49.8 ^(a)melt viscosity (in poise) unlessotherwise stated, otherwise relative viscosity (RV) b: on the basis of100 mol of balanced polymer

Polyamide material P is withdrawn at a rate of about 250 lb/hr as astream from the lowest stage of the reactor, and the composition of thatstream analysed by NIR spectroscopy. A trim feed of HMD at a rate of 0.7lb/hr is introduced into the stream of polyamide material P on the basisof the NIR analysis, and the composition of the polyamide material Panalysed immediately thereafter, providing a balanced polyamidematerial.

EXAMPLE 2 (COMPARATIVE) Column Without Sparging is Made at 15.5 InchInternal Diameter

A unit is designed for a nominal polymer production rate of 250 poundsper hour of nylon-6.6. A ten stage column is designed having 15.5 inchinternal diameter. The top nine stages are fitted with weirs to regulatethe liquid inventory on each stage such that the hold-up time on eachstage averages about 15 minutes. The inventory on the lowest stage isregulated by controlling the speed of the outlet pump.

Each stage of the column is jacketed externally and fitted with internalheating coils, all of which is used to regulate temperature of liquidmelt pools and is capable of separate temperature settings for everystage. Temperatures are set to maintain the liquid pools as a clear melton every stage, ending with the lowest part of the column at about 275°C.

The column is operated such that the top stage is at atmosphericcondition.

The column is fitted with agitators on the lowest two stages, designedto turn at between 15 and 50 rpm and impart a gentle blending of themelt pools. Both agitator blades are mounted on a single shaft which isfitted from below the column. The agitator shaft runs up thecentrally-located downcomer connecting the lowest stage with the nexthighest stage. The agitator runs at 30 rpm in this example, which issufficient in this design to recirculate the inventory within the meltpools ca. 10 times during the fifteen minute residence time.

A molten acid-rich mixture comprising 81 wt % adipic acid and 19 wt %hexamethylenediamine is fed to the top most stage of the column at arate of 90.7 kg/hr and at 130° C. Vapourised hexamethylenediamine is fedat a total rate of 40.4 kg/hr into the vapour-space of the lowest threestages. The distribution of the vapourised HMD feed is controlled suchthat 25 wt % is metered to the head-space of Stage 3, 70 wt % is meteredto the head-space of stage 2, and 5 wt % is metered to the head-space ofStage 1. In this example the HMD contained 5 wt % water such that thevapour feed also included 2.1 kg/hr of moisture. It is generally foundthe column operates equally well without water in the feed or withsteam.

Operating in these conditions, a melt of nylon-6,6 is producedexhibiting a relative viscosity of 20.4 and a difference-of-ends ofabout 80 eq/10⁶ g of polymer.

EXAMPLE 3 Column with Steam Sparging Made at 15.5 Inch Internal Diameter

A unit is designed for a nominal polymer production rate of 250 poundsper hour. A ten stage column is designed having 15.5 inch internaldiameter for the top nine stages. The lowest stage smoothly reducesdiameter in the head space down to a liquid inventory section having aconstant internal diameter of 12 inches and a working depth of 24 inches(similar to that shown in FIG. 3g ). The top nine stages are fitted withweirs to regulate the liquid inventory on each stage such that thehold-up time on each stage averages about 15 minutes. The inventory onthe lowest stage is regulated by controlling the speed of the outletpump.

This unit is fitted with temperature regulating jackets and coilsidentical to those of example 1. The temperature of the melt is againcontrolled.to reach 275° C. in the lowest stage.

The column is fitted with an agitator on the lowest stage, designed toturn at between 15 and 50 rpm and impart a gentle blending of the meltpool. The agitator blade is mounted on a single shaft which is fittedfrom below the column. There is no mechanical agitation on the secondstage in this example. The agitator runs at 30 rpm in this example,sufficient for the ten times recirculation level.

A molten acid-rich mixture comprising 81 wt % adipic acid and 19 wt %hexamethylenediamine is fed to the top most stage of the column at arate of 90.7 kg/hr and at 130° C. Vapourised hexamethylenediamine is fedat a total rate of 40.4 kg/hr into the vapour-space of the lowest threestages. The distribution of the vapourised HMD feed is controlled suchthat 25 wt % is metered to the head-space of Stage 3, 70 wt % is meteredto the head-space of stage 2, and 5 wt % is metered to the head-space ofStage 1. In this example the HMD contained 5 wt % water such that thevapour feed also included 2.1 kg/hr of moisture. It is generally foundthe column operates equally well without water in the feed or withsteam.

In addition to the those streams, an additional 1 kg/hr of super-heatedsteam is metered into the head space of the lowest stage. Thisadditional vapour supplements the largely HMD vapour feed such that therising vapour recirculates the liquid melt of Stage 2 approximately 10.7times during an average residence time of fifteen minutes.

Operating in these conditions, a melt of nylon-6,6 is producedexhibiting a relative viscosity of 20.5 and a difference-of-ends ofabout 80 eq/10⁶ g of polymer.

EXAMPLE 4 Column with Steam Sparging Made at 15.5 Inch Internal Diameter

A unit is designed for a nominal polymer production rate of 250 poundsper hour. A ten stage column is designed having 15.5 inch internaldiameter for the top nine stages. The lowest stage is described by FIG.3f with an unsparged but agitated conical section within a surroundingsparged melt pool. As shown in FIG. 3f , the lowest stage is also fittedwith a plenum enabling the introduction of vapour through the melt pool.The top nine stages are fitted with weirs to regulate the liquidinventory on each stage such that the hold-up time on each stageaverages about 15 minutes. The inventory on the lowest stage isregulated by controlling the speed of the outlet pump.

This unit is fitted with temperature regulating jackets and coilsidentical to those of example 1. The temperature of the melt is againcontrolled.to reach 275° C. in the lowest stage.

The column is fitted with an agitator only within the conical section ofthe lowest stage, designed to turn at between 15 and 50 rpm and impart agentle blending of the melt pool. The agitator blade is mounted on asingle shaft which is fitted from below the column. There is nomechanical agitation on the second stage in this example nor within thesurrounding sparged volume. The agitator runs at 30 rpm in this example,sufficient for the ten times recirculation level.

A molten acid-rich mixture comprising 81 wt % adipic acid and 19 wt %hexamethylenediamine is fed to the top most stage of the column at arate of 90.7 kg/hr and at 130° C. Vapourised hexamethylenediamine is fedat a total rate of 40.4 kg/hr into the vapour-space of the lowest threestages. The distribution of the vapourised HMD feed is controlled suchthat 25 wt % is metered to the head-space of Stage 3, 70 wt % is meteredto the head-space of stage 2, and 5 wt % is metered to the head-space ofStage 1. In this example the HMD contained 5 wt % water such that thevapour feed also included 2.1 kg/hr of moisture. It is generally foundthe column operates equally well without water in the feed or withsteam.

In addition to those streams, an additional 1.15 kg/hr of super-heatedsteam is metered via the plenum from beneath the lowest stage. Thisadditional vapour supplements the largely HMD vapour feed such that therising vapour recirculates the liquid melt of Stage 1a approximately10.3 times during an average residence time of fifteen minutes.

Operating in these conditions, a melt of nylon 6,6 is producedexhibiting a relative viscosity of 20.6 and a difference-of-ends ofabout 80 eq/10⁶ g of polymer.

EXAMPLE 5 A Large Column with a Modest Agitator

A unit is designed for a nominal polymer production rate of 20,200pounds per hour. A ten stage column is designed having 90 inch internaldiameter for the top nine stages. The lowest stage is described by FIG.3f with an unsparged but agitated conical section within a surroundingsparged melt pool. As shown in FIG. 3f , the lowest stage is also fittedwith a plenum enabling the introduction of vapour through the melt pool.The top nine stages are fitted with weirs to regulate the liquidinventory on each stage such that the hold-up time on each stageaverages about 15 minutes. The inventory on the lowest stage isregulated by controlling the speed of the outlet pump.

This unit is fitted with temperature regulating jackets and coilssimilar to those of example 1 but sized for this larger column. Thetemperature of the melt is again controlled.to reach 275° C. in thelowest stage.

The column is fitted with an agitator only within the conical section ofthe lowest stage, designed to turn at between 15 and 50 rpm and impart agentle blending of the melt pool. The agitator blade is mounted on asingle shaft which is fitted from below the column. There is nomechanical agitation on the second stage in this example nor within thesurrounding sparged volume. The agitator runs at 30 rpm in this example,sufficient for the ten times recirculation level.

A molten acid-rich mixture comprising 81 wt % adipic acid and 19 wt %hexamethylenediamine is fed to the top most stage of the column at arate of 7344.8 kg/hr and at 130° C. Vapourised hexamethylenediamine isfed at a total rate of 3267 kg/hr into the vapour-space of the lowestthree stages. The distribution of the vapourised HMD feed is controlledsuch that 25 wt % is metered to the head-space of Stage 3, 45 wt % ismetered to the head-space of stage 2, and 30 wt % is metered to thehead-space of Stage 1. In this example the HMD contained 5 wt % watersuch that the vapour feed also included 171.9 kg/hr of moisture. It isgenerally found the column operates equally well without water in thefeed or with steam.

In addition to the those streams, an additional 145 kg/hr ofsuper-heated steam is metered via the plenum from beneath the loweststage. This additional vapour supplements the largely HMD vapour feedsuch that the rising vapour recirculates the liquid melt of Stage 1approximately 10.2 times during an average residence time of fifteenminutes.

Operating in these conditions, a melt of nylon 6,6 is producedexhibiting a relative viscosity of 20.2 and a difference-of-ends ofabout 80 eq/10⁶ g of polymer.

A large production unit similar to that of Example 1 would require twoagitators of near 90 inch diameter sufficient to gently blend nearly 60inch deep liquid pools. This example only requires a single agitatorwithin a cone that is 10 inches at the bottom and 20 inches at the topinlet. This imparts a large capital savings and improvement inoperational reliability.

1. A continuous process for the manufacture of a polyamide, the processcomprising the steps of: flowing a stream A comprising a moltendicarboxylic acid, or a molten dicarboxylic acid-rich mixture comprisinga dicarboxylic acid and a diamine, through a first stage and at leastone more reaction stage of a vertical multistage reactor, wherein thefirst stage is at the top of the reactor; (ii) counter-currently flowinga stream B comprising a diamine as either a vapour or a diamine-richliquid through at least one of the stages below the first reaction stageof said vertical multistage reactor; (iii) accumulating a liquid phasematerial P comprising polyamide at and/or below the final stage of saidreactor; wherein said reactor is equipped with internal featuressuitable for effecting contact between counter-currently flowing streamsA and B; and wherein said process further comprises the step ofagitating said liquid phase material P by injecting a gaseous stream Ccomprising steam, or at least one inert gas, or a mixture of steam andat least one inert gas into the reactor at or below the final stage ofthe reactor.
 2. The process of claim 1, wherein gaseous stream Cconsists or consists essentially of steam.
 3. The process of claim 1 orclaim 2, wherein the gaseous stream C is injected at a rate of at least5 kg/hr per million grams of polyamide produced per hour, preferably atleast about 8 kg/hr per million grams of polyamide produced per hour. 4.The process of any preceding claim, wherein the viscosity of said liquidphase material P is controlled by directly controlling the chemicalequilibrium of the polyamidation reaction in the reactor or bycontrolling stream B so that the amounts of diamine and dicarboxylicacid introduced into the reactor during the process arestoichiometrically imbalanced, and preferably wherein said viscosity ofsaid liquid phase material P is maintained at a value of no more thanabout 1200 poise, preferably no more than about 500 poise, andpreferably in the range of from about 0.1 to about 200 poise.
 5. Theprocess of claim 4, wherein the chemical equilibrium is controlled byinjecting a stream comprising steam into at least one of the stagesbelow said first reaction stage of said vertical multistage reactor. 6.The process of claim 5, wherein the stream comprising steam is saidstream C or a stream D.
 7. The process of claim 6, wherein said stream Dis injected into at least one of the stages below said first reactionstage of said vertical multistage reactor.
 8. The process of claim 5 or6, wherein said stream D further comprises at least one inert gas. 9.The process of any preceding claim, wherein the reactor is operatedunder atmospheric pressure or below atmospheric pressure.
 10. Theprocess of any of claims 4 to 8, wherein the chemical equilibrium iscontrolled by maintaining the pressure of the reactor at a pressuregreater than atmospheric pressure.
 11. The process of claim 10 whereinthe reactor is maintained at a pressure of at least about 1.5 atm, andpreferably no more than about 20 atm, and preferably in the range offrom about 5 atm to about 12 atm.
 12. The process of any precedingclaim, wherein the moisture concentration of the liquid phase material Pis maintained at a level of at least 0.1 wt %, preferably at least 0.2wt %, preferably at least 0.3 wt % and preferably no more than 3.0 wt %.13. The process of any of claims 4 to 12, wherein viscosity iscontrolled by controlling stream B so that the diamine and dicarboxylicacid introduced into the reactor are stoichiometrically imbalanced. 14.The process of claim 13, wherein an excess of dicarboxylic acid overdiamine is introduced into the reactor during the process, preferablywherein the stoichiometric imbalance in the liquid phase material P issuch that the molar ratio of [moles dicarboxylic acid units]: [moles ofdiamine units] is no more than 1.3:1, preferably no more than 1.1:1, andpreferably no more than 1.05:1, and preferably at least 1.005:1.
 15. Theprocess of any preceding claim, wherein the dicarboxylic acid includesone or more diacids selected from the group consisting of oxalic acid,malonic acid, succinic acid, glutaric acid, pimelic acid, adipic acid,suberic acid, azelaic acid, sebacic acid, undecanedioic acid,dodecandioic acid, maleic acid, glutaconic acid, traumatic acid, andmuconic acid, 1,2- or 1,3-cyclohexande dicarboxylic acids, 1,2- or1,3-phenylenediacetic acids, 1,2- or 1,3-cyclohexane diacetic acids,isophthalic acid, terephthalic acid, 4,4′-oxybisbenzoic acid,4,4-benzophenone dicarboxylic acid, 2,6-napthalene dicarboxylic acid,p-t-butyl isophthalic acid and 2,5-furandicarboxylic acid.
 16. Theprocess of any preceding claim, wherein the diamine is elected from thegroup consisting of ethanoldiamine, trimethylenediamine, putrescine,cadaverine, hexamethyelenediamine, 2-methyl pentamethylenediamine,heptamethylenediamine, 2-methyl hexamethylenediamine, 3-methylhexamethylenediamine, 2,2-dimethyl pentamethylenediamine,octamethylenediamine, 2,5-dimethyl hexamethylenediamine,nonamethylenediamine, 2,2,4- and 2,4,4-trimethyl hexamethylenediamines,decamethylenediamine, 5-methylnonanediamine, isophoronediamine,undecamethylenediamine, dodecamethylenediamine, 2,2,7,7-tetramethyloctamethylenediamine, meta-xylylene diamine, paraxylylene diamine,bis(p-aminocyclohexyl)methane, bix(aminomethyl)norbornane, any C₂-C₁₆aliphatic diamine optionally substituted with one or more C₁ to C₄ alkylgroups, aliphatic polyether diamines and furanic diamines such as2,5-bis(aminomethyl)furan.
 17. The process of any preceding claimwherein the dicarboxylic acid is adipic acid and the diamine ishexamethylenediamine.
 18. The process of any preceding claim, whereinthe vertical multistage reactor has at least 6 and/or no more than 10stages.
 19. The process of any preceding claim, wherein each stage ofthe reactor comprises a horizontal plate, a vertical channel and a weir,preferably wherein said plate comprises perforations therein.
 20. Avertical multistage reactor suitable for implementing the process ofclaims 1 to 19 wherein the reactor comprises: (i) a first stage; (ii) atleast one stage below the first stage; (iii) internal features suitablefor effecting contact between counter-currently flowing streams of afirst stream A introduced through the first stage and a second stream Bintroduced through at least one of the stages below the first reactionstage; and (iv) a chamber configured to allow a gaseous stream C to beinjected from the chamber into the reactor at or below the final stageof the reactor.
 21. The vertical multistage reactor of claim 20, whereinsaid chamber is located below the final stage.
 22. The verticalmultistage reactor of claim 20 or 21, wherein said gaseous stream Cconsists, or consists essentially of, steam.
 23. The vertical multistagereactor of any of claims 20 to 22, wherein said internal featurescomprise a horizontal plate, a vertical channel and a weir, preferablywherein said plate comprises perforations therein, and wherein each ofsaid stages comprises said internal features.
 24. The verticalmultistage reactor of claim 23 further comprising a vapour deflectorconfigured to reduce or prevent gas passing upwardly through saidchannel.
 25. The vertical multistage reactor of any one of claims 23 to24, wherein at least one of said channels in the reactor is acylindrical pipe.
 26. The vertical multistage reactor of any of claims20 to 25, wherein at least one of said channels in the reactor is anannular region defined at least partly by a wall of the reactor.
 27. Thevertical multistage reactor of any one of claims 20 to 26 comprising atleast 4 stages wherein said stages are alternating stages of a firstconfiguration and a second configuration, wherein in use a reactionfluid flows through a stage having said first configuration by passingover a weir into a cylindrical pipe and into a subsequent stage whichhas a second configuration, wherein reaction fluid flows through saidstage having a second configuration by passing over a weir into anannular region defined at least partly by the wall of the reactor andinto a subsequent stage which has said first configuration.
 28. Thevertical multistage reactor of any of claims 20 to 27, wherein thereactor further comprises a conical region in which liquid phasematerial accumulates during use of the reactor.
 29. The verticalmultistage reactor of claim 28, wherein a mechanical agitator isdisposed in said conical region.
 30. The vertical multistage reactor ofany of claims 20 to 29 configured to implement the process of any one ofclaims 1 to 18.